CN101310203A - Phase-difference layer laminated polarizing plate, liquid crystal panel, and liquid crystal display device - Google Patents

Abstract

This invention provides a polarizing plate with a phase difference layer, which has excellent double side contrast and can suppress uneven display caused under a high-temperature environment, and a liquid crystal panel and a liquid crystal display device. The polarizing plate with a phase difference layer comprises a pressure-sensitive adhesive layer, a phase difference layer comprising a resin layer and a slant alignment layer, and a polarizer provided in that order. The holding power (HA) of the pressure-sensitive adhesive layer at 60 C is not more than 300 [mu]m, and the direction of a slow phase axis of the phase difference layer is substantially perpendicular to the direction of an absorption axis of the polarizer. The slant alignment layer is formed of a liquid crystal composition containing a discotic compound which is in a slant aligned state.

Description

The polaroid, liquid crystal panel and the liquid crystal indicator that have phase separation layer

Technical field

The present invention relates to have the polaroid of phase separation layer, the liquid crystal panel that has used this polaroid that has phase separation layer and liquid crystal indicator.Say that in more detail it is outstanding and can be suppressed at polaroid, liquid crystal panel and the liquid crystal indicator of the band phase separation layer of the demonstration inequality that produces under the hot environment to the present invention relates to picture contrast.

Background technology

In various image display devices such as liquid crystal indicator or electroluminescence (EL) display, in order to carry out optical compensation, use the various polaroids that have phase separation layer that made up polariscope and phase separation layer usually.For example, can enumerate polaroid (for example, with reference to patent documentation 1) with the phase separation layer that forms by discoid (discotic) liquid-crystalline polymer.

When use has the polaroid of phase separation layer in liquid crystal indicator, normally be attached on the liquid crystal cells by adhesive layer, show uneven problem but have under hot environment, to produce.And then, also have the problem that produces light leak, contrast reduction at the edge of picture.

Patent documentation 1: the spy opens flat 7-134213 communique

Summary of the invention

The present invention just for address the above problem and the invention finished, its purpose is, provides a kind of picture contrast outstanding and can be suppressed at the polaroid that has phase separation layer of the demonstration inequality that takes place under the hot environment, the liquid crystal panel that has used this polaroid that has phase separation layer and liquid crystal indicator.

The polaroid that has phase separation layer of the present invention is by having adhesive phase successively, containing the phase separation layer and the polariscope of resin bed and tilted alignment layer, the confining force (H of this adhesive phase under 60 ℃ _A) be below the 300 μ m, the slow axis direction of this phase separation layer and the basic quadrature of this polariscopic absorption axes direction, this tilted alignment layer is to be formed by the liquid crystalline composition that contains discoid compound, and this discoid compound is a tilted alignment.

In preferred embodiment, the confining force (H of above-mentioned adhesive phase under 60 ℃ _A) and the confining force (H under 23 ℃ _B) poor (H _A-H _B) be below the 100 μ m.

In preferred embodiment, the moisture rate of above-mentioned adhesive phase is below 1.0%.

In preferred embodiment, the gel fraction of above-mentioned adhesive phase is more than 75%.

In preferred embodiment, above-mentioned adhesive phase is that the adhesive composition that contains (methyl) acryloyl based polymer (A) and superoxide (B) by making at least carries out crosslinked formation.

In preferred embodiment, above-mentioned (methyl) acryloyl based polymer (A) is the multipolymer of (methyl) alkyl acrylate (a1) and hydroxyl (methyl) acrylate (a2).

In preferred embodiment, the use level of above-mentioned superoxide (B) is 0.01～1 weight portion with respect to above-mentioned (methyl) acryloyl based polymer (A) 100 weight portions.

In preferred embodiment, above-mentioned adhesive composition also contains the isocyanates based compound.

In preferred embodiment, the use level of above-mentioned isocyanates based compound is 0.04～1 weight portion with respect to above-mentioned (methyl) acryloyl based polymer (A) 100 weight portions.

In preferred embodiment, the index ellipsoid of above-mentioned resin bed has the relation of nx 〉=ny＞nz.

In preferred embodiment, above-mentioned resin bed is the polymeric membrane that contains cellulose-based resin.

In preferred embodiment, above-mentioned discoid compound is that benzophenanthrene (triphenylene) is discoid compound.

In preferred embodiment, phase differential Re[590 in the face of above-mentioned phase separation layer] be 20～80nm.

In preferred embodiment, the thickness direction phase differential Rth[590 of above-mentioned phase separation layer] be 100～300nm.

In preferred embodiment, the Nz coefficient of above-mentioned phase separation layer is 2～8.

In preferred embodiment, the average tilt angle of above-mentioned phase separation layer is 8～24 °.

In preferred embodiment, above-mentioned polariscope is to be the oriented film of principal ingredient with the polyvinyl alcohol resin that contains iodine or dichroic dye.

According to other embodiments of the present invention, provide liquid crystal panel.This liquid crystal panel comprises: liquid crystal cells, be configured in a side of this liquid crystal cells and above-mentionedly have the polaroid of phase separation layer and dispose the opposite side of this liquid crystal cells and above-mentioned adhesive phase is configured to the above-mentioned polaroid that has phase separation layer of liquid crystal cell side what above-mentioned adhesive phase was configured to liquid crystal cell side.

In preferred embodiment, above-mentioned liquid crystal cells is the TN pattern.

According to other embodiments of the present invention, provide liquid crystal indicator.This liquid crystal indicator comprises above-mentioned liquid crystal panel.

As mentioned above, according to the present invention, by making up specific phase separation layer and specific adhesive phase, can provide picture contrast outstanding and at the polaroid that has phase separation layer, liquid crystal panel and the liquid crystal indicator that can be suppressed at the demonstration inequality that takes place under the hot environment.

Description of drawings

Fig. 1 is the fragmentary cross sectional view of the polaroid that has phase separation layer of preferred implementation of the present invention.

Fig. 2 is the exploded perspective view of the polaroid that has phase separation layer of preferred implementation of the present invention.

Fig. 3 is the mode chart of notion of representing the representative manufacturing process of the adhesive phase that uses in the present invention.

Fig. 4 is a mode chart of representing the notion of the polariscopic representative manufacturing process that uses in the present invention.

Fig. 5 is the fragmentary cross sectional view of the liquid crystal panel of preferred implementation of the present invention.

Fig. 6 is the fragmentary cross sectional view of expression state of orientation of the liquid crystal molecule of explanation liquid crystal layer when liquid crystal panel of the present invention adopts the liquid crystal cells of TN pattern.

Fig. 7 is the disassembled schematic that the optical axis of the liquid crystal panel of expression preferred implementation of the present invention concerns.

Fig. 8 is the sketch of the assay method of expression confining force.

Fig. 9 (a) is the dependent contrast contour map of field angle of contrast of the polaroid that has phase separation layer of expression embodiments of the invention 1, (b) be the dependent contrast contour map of field angle of contrast of the polaroid that has phase separation layer of expression embodiments of the invention 3, (c) being the dependent contrast contour map of field angle of contrast of the polaroid that has phase separation layer of expression embodiments of the invention 4, (d) is the dependent contrast contour map of field angle of contrast of the polaroid of expression comparative example 2.

Figure 10 (a) is the dependent curve map of polar angle of contrast ratio of the polaroid of expression polaroid that has phase separation layer of embodiments of the invention 1,3,4 and comparative example 2, (b) is the dependent curve map in position angle of contrast ratio of the polaroid of the polaroid that has phase separation layer of expression embodiments of the invention 1,3,4 and comparative example 1.

Observation photo when Figure 11 (a) is the demonstration picture black of liquid crystal indicator of embodiments of the invention 1, observation photo when being the demonstration picture black of liquid crystal indicator of embodiments of the invention 2 (b), the observation photo when being the demonstration picture black of liquid crystal indicator of comparative example 1 (c).

Among the figure: 10,10 '-adhesive phase

20,20 '-phase separation layer

21,21 '-resin bed

22,22 '-tilted alignment layer

30,30 '-polariscope

The 40-liquid crystal cells

41,42-substrate

The 43-liquid crystal layer

The 44-separator

100,100 '-have a polaroid of phase separation layer

The 101-liquid crystal panel

Embodiment

(definition of term and symbol)

Shown in term and symbol are defined as follows in this instructions.

(1) " nx " is that refractive index in the face is the refractive index of maximum direction (being the slow axis direction), and " ny " is the refractive index of direction (being the leading phase shaft direction) vertical with slow axis in face, and " nz " is the refractive index of thickness direction.In addition, for example " nx=ny " not only comprises nx and the strict situation about equating of ny, also comprises the situation that nx and ny equate substantially.In this manual, the whole polarization characteristic that " equal substantially " is also included within not the polaroid that has phase separation layer brings in the scope of the influence in the practicality, perhaps bring in the scope of the influence in the practicality situation that nx is different with ny at whole display characteristic not to liquid crystal panel.

(2) phase differential Re[590 in the face] be meant under 23 ℃ with the phase difference value in film (layer) face of the light measurement of wavelength 590nm.Re[590] be respectively nx, ny in the slow axis direction of the film that makes wavelength 590nm place respectively (layer), the refractive index of leading phase shaft direction, when the thickness that makes film (layer) is d (nm), utilize formula: Re=(nx-ny) * d and obtaining.

(3) the phase differential Rth[590 of thickness direction] be meant under 23 ℃ phase difference value with the thickness direction of the light measurement of wavelength 590nm.Rth[590] be respectively nx, nz in the slow axis direction of the film that makes wavelength 590nm place (layer), the refractive index of thickness direction, when the thickness that makes film (layer) is d (nm), utilize formula: Re=(nx-nz) * d and obtaining.Wherein, slow axis is meant that refractive index is maximum direction in the face.

Below, preferred implementation of the present invention is described, but the present invention is not limited to these embodiments.

A. the integral body that has the polaroid of phase separation layer constitutes

Fig. 1 is the fragmentary cross sectional view of the polaroid that has phase separation layer of preferred implementation of the present invention.This polaroid 100 that has phase separation layer has adhesive phase 10, phase separation layer 20 and polariscope 30 successively.Phase separation layer 20 comprises resin bed 21 and tilted alignment layer 22.In Fig. 1 (a), tilted alignment layer 22 is configured to adhesive phase 10 sides, but shown in Fig. 1 (b), tilted alignment layer 22 can also be configured to polariscope 30 sides.Preferred phase separation layer 20 is configured to tilted alignment layer 22 and is adhesive phase 10 sides.By configuration like this, for example when being used for liquid crystal indicator, can suitably carry out the optical compensation of liquid crystal cells, obtain positive and the oblique high liquid crystal indicator of contrast ratio.

The basic quadrature of absorption axes direction of the slow axis direction of phase separation layer 20 and polariscope described later 30.In this manual, " basic quadrature " is meant that the absorption axes direction angulation of the slow axis direction of phase separation layer 20 and above-mentioned polariscope 30 is 90 ° ± 2.0 ° a scope.Preferred 90 ° ± 1.0 °, further preferred 90 ° ± 0.5 °.

In one embodiment, one side the slow axis direction of phase separation layer 20 is 45 ° (or 135 °) (with reference to Fig. 2 (a)) with respect to the polaroid that has phase separation layer.In other embodiments, one side the slow axis direction of phase separation layer 20 is 90 ° (or 0 °) (with reference to Fig. 2 (b)) with respect to the polaroid that has phase separation layer.Shown in Fig. 2 (a), be 45 ° (or 135 °) with respect to the polaroid that has phase separation layer one side phase separation layer 20 is configured to its slow axis direction.The polaroid that has phase separation layer like this when being used for liquid crystal indicator, can especially increase the contrast ratio of frontal.And then, when oblique observation picture, observe to obtain certain contrast ratio from any orientation of 360 °.

B. adhesive phase

B-1. the summary of adhesive phase

Confining force (the H of above-mentioned adhesive phase 10 under 60 ℃ _A) be below the 300 μ m, be preferably 50～300 μ m, more preferably 60～250 μ m are preferably 70～200 μ m especially.If confining force (H _A) be this scope, the demonstration inequality that can suppress to take place under the hot environment.

Confining force (the H of above-mentioned adhesive phase under 60 ℃ _A) and the confining force (H under 23 ℃ _B) poor (H _A-H _B) be preferably below the 100 μ m, more preferably 10～90 μ m are preferably 20～80 μ m especially, most preferably are 30～70 μ m.As long as (H _A-H _B) in such scope, can more effectively be suppressed at the demonstration inequality that takes place under the hot environment.

The thickness of above-mentioned adhesive phase can suitably be set according to purpose.Thickness is preferably 2～50 μ m, and more preferably 2 μ m～40 μ m are preferably 5 μ m～35 μ m especially.By thickness setting being become such scope, can obtain having suitable cementability and the outstanding adhesive phase of fissility.

The transmitance with the light measurement of wavelength 590nm under 23 ℃ of above-mentioned adhesive phase is preferably more than 90%.Transmitance in theory on be limited to 100%, be limited to 96% in the practicality.

The gel fraction of above-mentioned adhesive phase is preferred more than 75%, and further preferred 75%～90%, preferred especially 80%～85%.By making gel fraction in above-mentioned scope, can obtain having the adhesive phase of excellent bonds characteristic.Gel fraction can wait suitably and regulate by kind, the content of the crosslinking chemical that uses.Usually, the polymkeric substance of bonding agent is cross-linked to form the part of tridimensional network (being also referred to as gel section), and in the time of in being immersed in solvent, lyosorption increases volume.This phenomenon is called swelling.

The glass temperature of above-mentioned adhesive phase (Tg) is preferably-70 ℃～-10 ℃, more preferably-60 ℃～-20 ℃, be preferably-50 ℃～-30 ℃ especially.By making glass temperature is above-mentioned scope, can obtain phase separation layer is had the adhesive phase of strong bond.In addition, when the substrate that is laminated in liquid crystal cells (glass plate), can obtain having appropriate cementability and the outstanding adhesive phase of fissility.

The moisture rate of above-mentioned adhesive phase is preferably below 1.0%, more preferably below 0.8%, is preferably especially below 0.6%, most preferably is below 0.4%.Moisture rate lower limit in theory is 0.By making moisture rate is above-mentioned scope, even if can obtain also being difficult to the adhesive phase that foams under hot environment.

As long as above-mentioned adhesive phase satisfies aforesaid confining force (H _A), can form by any suitable material.As object lesson, crosslinked and adhesive phase that form describes to making adhesive composition.About this adhesive composition, as described later.Wherein, in this manual, " making crosslinked " is meant that polymkeric substance generation chemical crosslinking forms tridimensional network.

Above-mentioned adhesive phase can also contain suitable any composition, as any composition, for example can enumerate metal powder, glass fibre, beaded glass, silicon dioxide, filling agent etc.Arbitrarily the content of composition is with respect to total solid composition 100 weight portions that form above-mentioned adhesive phase, preferably surpasses 0 and be below 10 weight portions, and then preferably surpasses 0 and be below 5 weight portions.In addition, above-mentioned adhesive phase can also contain the material of dividing a word with a hyphen at the end of a line (for example residual solvent, adjuvant, oligomer etc.) from adjacent layer.

B-2. adhesive composition

Above-mentioned adhesive composition contains (methyl) acryloyl based polymer (A) and superoxide (B) at least.(methyl) acryloyl based polymer (A) is meant by acrylic ester monomer and/or synthetic polymkeric substance or the multipolymer of methacrylate ester monomer (being called in this manual, (methyl) acrylate).When (methyl) acryloyl based polymer (A) is multipolymer, the ordered state of its molecule is not particularly limited, can be random copolymers, also can be segmented copolymer, can also be graft copolymer.The preferred molecules align state of above-mentioned (methyl) acryloyl based polymer (A) is a random copolymers.

(methyl) acryloyl based polymer (A) for example can obtain by (being total to) polymerization (methyl) alkyl acrylate (a1).

The alkyl of (methyl) alkyl acrylate (a1) can be the straight chain shape, also can be a chain, can also be ring-type.The carbon number of the alkyl of (methyl) alkyl acrylate (a1) is preferably about 1～18, and more preferably 1～10.

As the object lesson of (methyl) alkyl acrylate (a1), can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid isopentyl ester, the just own ester of (methyl) acrylic acid, (methyl) Isohexyl acrylate, the positive heptyl ester of (methyl) acrylic acid, (methyl) acrylic acid isocyanate, (methyl) 2-EHA, (methyl) acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) dodecylacrylate, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate.They can use separately, can also be used in combination more than 2 kinds.When combination was more than 2 kinds, the average carbon atom number of the alkyl of (methyl) alkyl acrylate (a1) was preferably 3～9.

(methyl) acrylic acid series polymeric compounds (A) preferably makes above-mentioned (methyl) alkyl acrylate (a1) and hydroxyl (methyl) acrylate (a2) that copolymerization takes place and obtains.By using such multipolymer, outstanding with the reactivity of superoxide (B), so can obtain having outstanding fusible adhesive phase.At this moment, the carbon number of the alkyl of (methyl) alkyl acrylate (a1) is preferably 1～8, and more preferably 2～8, be preferably 2～6 especially, most preferably be 4～6.The alkyl of (methyl) alkyl acrylate (a1) can be the straight chain shape, can also be a chain.

As the object lesson of above-mentioned hydroxyl (methyl) acrylate (a2), can enumerate (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 3-hydroxy butyl ester, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 5-hydroxy pentane ester, (methyl) acrylic acid 3-hydroxy-3-methyl butyl ester, the own ester of (methyl) acrylic acid 6-hydroxyl, (methyl) acrylic acid 7-hydroxyl heptyl ester, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 12-hydroxyl dodecyl ester, acrylic acid (4-hydroxymethyl cyclohexyl)-methyl esters etc.They can use separately, can also be used in combination more than 2 kinds.

The carbon number of the hydroxyalkyl of hydroxyl (methyl) acrylate (a2) is preferably identical with the carbon number of the alkyl of (methyl) alkyl acrylate (a1) or more than it.And then the carbon number of the hydroxyalkyl of hydroxyl (methyl) acrylate (a2) is preferably 2～8, more preferably 4～6.Thus, by regulating carbon number, can improve the reactivity with superoxide (B), and then can obtain having outstanding fusible adhesive phase.And then, outstanding with the reactivity of isocyanates based compound described later (C).For example as hydroxyl (methyl) acrylate (a2), when using (methyl) acrylic acid 4-hydroxy butyl ester, preferred (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate or (methyl) butyl acrylate of using is as (methyl) alkyl acrylate (a1).

The copolymerization amount of hydroxyl (methyl) acrylate (a2) is preferably 0.1～10 mole of %, and more preferably 0.2～5 mole of % is preferably 0.3～1.1 mole of % especially.So long as the copolymerization amount of above-mentioned scope just can obtain connecting airtight property, permanance, the outstanding adhesive phase of stress retentivity.

Above-mentioned (methyl) acrylic acid series polymeric compounds (A) except above-mentioned (methyl) alkyl acrylate (a1), hydroxyl (methyl) acrylate (a2), can also obtain by making other composition copolymerization.As other compositions, be not particularly limited preferred (methyl) benzyl acrylate, (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid ethoxy methyl esters, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylamide, vinyl acetate, (methyl) vinyl cyanide etc. of using.The copolymerization amount of other compositions is below 100 weight portions with respect to (methyl) alkyl acrylate (a1) 100 weight portions preferably, more preferably below 50 weight portions.

The weight-average molecular weight (Mw) of (methyl) acrylic acid series polymeric compounds (A) is preferably more than 1,000,000, and more preferably 1,200,000～3,000,000, be preferably 1,200,000～2,500,000 especially.Solvent when wherein, Mw can be by suitable selective polymerization, temperature, adjuvant described later etc. are adjusted.

(methyl) acrylic acid series polymeric compounds (A) can utilize any suitable method to make.For example, can suitably select radical polymerizations such as mass polymerization, mass polymerization, solution polymerization process, suspension polymerization.In radical polymerization, can use suitable arbitrarily radical polymerization initiator (for example azo system, peroxidating system).Temperature of reaction is generally about 50～80 ℃, and the reaction time is generally 1～30 hour.

In above-mentioned polymerization, the preferred solution polymerization.This is because can regulate the polymer solution polymerization temperature also easily takes out polymerization from reaction vessel after accurately.As the solvent that uses in the solution polymerization process, can enumerate ethyl acetate, toluene etc. usually.Solution concentration is generally about 20～80 weight %.Specify solution polymerization process.For example, monomer is dissolved in the solvent,, modulates solution with respect to the polymerization initiators such as azoisobutyronitrile of monomer 100 weight portions interpolation 0.01～0.2 weight portion.Then, under nitrogen atmosphere, set the temperature of solution for 50 ℃～70 ℃, make its reaction 8 hours～30 hours.

Above-mentioned superoxide (B) as long as can produce free radical under heating and realize the crosslinked of (methyl) acrylic acid series polymeric compounds (A), just is not particularly limited.As superoxide (B), for example can enumerate hydroperoxide kind, dialkyl peroxide class, peroxyesters, diacyl peroxide class, peroxy dicarbonate, ketal peroxide class, ketone peroxide class etc.Particularly; can enumerate two (2-ethylhexyl) peroxy dicarbonate; two (4-tert-butylcyclohexyl) peroxy dicarbonate; di-secondary butyl peroxyization two carbonic esters; tert-butyl hydroperoxide neodecanoic acid ester; uncle's hexyl peroxidating pivalate; t-butylperoxy pivarate; two lauroyl peroxides; two positive decoyl superoxide; 1; 1; 3; 3-tetramethyl butyl peroxidating-2 ethyl hexanoic acid ester; 1; 1; 3,3-tetramethyl butyl peroxidating isobutyrate; two (4-toluyl) superoxide; the dibenzoyl superoxide; the tert-butyl hydroperoxide butyric ester; methylbenzoyl peroxide between benzoyl; toluoyl base superoxide etc.These superoxide can use separately, can also make up more than 2 kinds and use.

In the middle of above-mentioned superoxide, preferably use the diacyl peroxide class, methylbenzoyl peroxide between further preferred dibenzoyl superoxide and/or benzoyl.These superoxide are because 1 minute described later half life temperature is 90 ℃～140 ℃, so have good storage stability and can control cross-linking reaction accurately.

As above-mentioned superoxide (B), can directly use commercially available product.Object lesson as commercially available product, can enumerate PEROYL series (trade name " IB, 335, L, SA, IPP, NPP, TCP etc. ", Japan's grease (strain) system), NYPER series (trade name " FF, BO, NS, E, BMT-Y, BMT-K40, BMT-M etc. ", Japanese grease (strain) system) etc.

The use level of above-mentioned superoxide (B) is preferably 0.01～1 weight portion with respect to (methyl) acrylic acid series polymeric compounds (A) 100 weight portions, 0.05～0.8 weight portion more preferably, be preferably 0.1～0.5 weight portion especially, most preferably be 0.15～0.45 weight portion.By the use level that makes superoxide (B) is above-mentioned scope, and adhesive phase can be realized above-mentioned confining force fully, and then can show the stress retentivity of appropriateness and outstanding thermal stability.Its result when being used for liquid crystal indicator, can effectively be suppressed at the demonstration inequality that produces under the hot environment.Wherein, contain superoxide, can obtain the little adhesive phase of moisture rate by making it.Moisture rate that it is generally acknowledged adhesive phase helps the reduction of the demonstration inequality of liquid crystal indicator for a short time.

Above-mentioned adhesive composition also preferably further contains the isocyanates based compound.This is because can improve the connecting airtight property (be also referred to as throw anchor-hold) of adhesive phase and phase separation layer.As the isocyanates based compound, can enumerate the isocyanate-monomers such as methyl diphenylene diisocyanate of toluene diisocyanate, chlorobenzene support diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methyl diphenylene diisocyanate, trimethylolpropane Xylene Diisocyanate, hydrogenation; The adduction system isocyanate compound that polyvalent alcohol additions such as these isocyanate-monomers and trimethylolpropane are obtained; The cyamelide ester compounds; Biuret type compound; And then can also enumerate the isocyanates etc. of the carbamate prepolymer type that generation addition reactions such as making arbitrarily suitable polyether glycol or polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyvalent alcohol obtains.They can use separately, can also be used in combination more than 2 kinds.Wherein, preferably use the trimethylolpropane Xylene Diisocyanate.This is because the connecting airtight property of adhesive phase and phase separation layer can further improve.

As above-mentioned isocyanates based compound, can directly use commercially available product.As commercially available isocyanates based compound, for example can enumerate the military field chemistry of Mitsui (strain) system ケ ネ one ト series (trade name " D-110N, 500,600,700 etc. "), Japanese polyurethane industry (strain) Coronate series (for example, trade name " L, MR, EH, HL etc. ") etc.

The use level of above-mentioned isocyanates based compound can be set suitable amount according to purpose.For example, use level is preferably 0.04～1 weight portion with respect to (methyl) acrylic acid series polymeric compounds (A) 100 weight portions, further preferred 0.06～0.8 weight portion, and preferred especially 0.08～0.6 weight portion most preferably is 0.1～0.2 weight portion.Use level by making the isocyanates based compound is in above-mentioned scope, and adhesive phase can be realized above-mentioned confining force fully, and then can show that the stress retentivity of appropriateness closes outstanding thermal stability.Its result when being used for liquid crystal indicator, can obtain the uneven little liquid crystal indicator of demonstration that produces under hot environment.And then even if under the environment of too harsh (high temperature, how wet), it is good that the connecting airtight property of adhesive phase and phase separation layer can become.It is generally acknowledged and use superoxide and isocyanates based compound also to help to reduce the demonstration inequality as crosslinking chemical.

Above-mentioned adhesive composition can also contain silane coupling agent.This is because when using the polaroid that has a phase separation layer of the present invention in liquid crystal indicator, the connecting airtight property of adhesive phase and liquid crystal cell substrate can improve.As silane coupling agent, can use to have arbitrarily the suitably material of functional group.As functional group, for example can enumerate vinyl, epoxy radicals, methacryloxy, amino, sulfydryl, acryloxy, acetoacetyl, isocyanate group, styryl, polysulfide base etc.Object lesson as silane coupling agent, can enumerate vinyltrimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, to the styryl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-acryloxy propyl trimethoxy silicane, the 3-TSL 8330, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl) 3-aminopropyl methyl dimethoxysilane, gamma-amino propyl group methoxy silane, γ-sulfydryl propyl group methyl dimethoxysilane, two (triethoxysilylpropyltetrasulfide) tetrasulfide, γ-isocyanates propyl trimethoxy silicane etc.Wherein, the preferred silane coupling agent that uses with acetoacetyl.This is because the connecting airtight property of adhesive phase and liquid crystal cell substrate can further improve.

As above-mentioned silane coupling agent, can directly use commercially available product.As commercially available silane coupling agent, for example can enumerate SHIN-ETSU HANTOTAI's silicone (strain) system KA series (trade name " KA-1003 etc. "), SHIN-ETSU HANTOTAI's silicone (strain) system KBM series (trade name " KBM-303, KBM-403, KBM-503 etc. "), SHIN-ETSU HANTOTAI's silicone (strain) system KBE series (trade name " KBE-402, KBE-502, KBE-903 etc. "), east beautiful (strain) system SH series (trade name " SH6020, SH6040, SH6062 etc. "), east beautiful (strain) system SZ series (trade name " SZ6030, SZ6032, SZ6300 etc. ").

The use level of above-mentioned silane coupling agent can suitably be set according to purpose.For example, use level is preferably 0.001～2 weight portion with respect to (methyl) acrylic acid series polymeric compounds (A) 100 weight portions, further preferred 0.005～2 weight portion, and preferred especially 0.01～1 weight portion most preferably is 0.02～0.5 weight portion.Use level by making silane coupling agent is in above-mentioned scope, even if under the environment of too harsh (high temperature, how wet), the connecting airtight property of adhesive phase and phase separation layer can be good.

Above-mentioned adhesive composition can also contain various adjuvants in the scope that does not break away from the object of the invention.As adjuvant, for example can enumerate plastifier, thermal stabilizer, light stabilizer, lubricant, antioxidant, ultraviolet light absorber, fire retardant, colorant, antistatic agent, appearanceization agent mutually, crosslinking chemical, tackifier, pigment etc.

The use level of above-mentioned other adjuvants can be set suitable amount according to purpose.Use level is preferably above 0 with respect to (methyl) acrylic acid series polymeric compounds (A) 100 weight portions and is below 5 weight portions.

Above-mentioned adhesive composition for example can utilize the method that contains following operation 1A and operation 1B to prepare.

Operation 1A: with solvent dilution above-mentioned (methyl) acrylic acid series polymeric compounds (A), the operation of preparation polymer solution (1-A),

Operation 1B: in the polymer solution that in operation 1A, obtains (1-A), cooperate above-mentioned superoxide (B), above-mentioned isocyanates based compound as required and/or the operation of above-mentioned adjuvant.

By using such method, can obtain more uniform adhesive composition.As the fitting method of each composition, can suitably adopt suitable method here.Preferably in polymer solution (1-A), add superoxide (B), isocyanates based compound, silane coupling agent successively.And then, when making (methyl) acrylic acid series polymeric compounds (A) polymerization with solution polymerization process, can directly use the reaction solution that obtains as above-mentioned polymer solution (1-A).Can also use the dilute solution that in obtaining reaction solution, has added solvent as polymer solution (1-A).

As the solvent that in above-mentioned modulation, uses,, just be not particularly limited so long as can dissolve the solvent of (methyl) acrylic acid series polymeric compounds (A).Particularly, can enumerate toluene, dimethylbenzene, chloroform, methylene chloride, ethylene dichloride, phenol, Anaesthetie Ether, tetrahydrofuran, anisole, tetrahydrofuran, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl-n-butyl ketone, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, normal butyl alcohol, the 2-butanols, cyclohexanol, isopropyl alcohol, tert-butyl group alcohol, glycerine, ethylene glycol, diethylene glycol dimethyl ether, 2-methyl-2,4-pentanediol dimethyl formamide, dimethyl acetamide, acetonitrile, butyronitrile, methyl cellosolve, methylcellosolve acetate, ethyl acetate, butyl acetate etc.They can use separately, can also be used in combination more than 2 kinds.Wherein, preferred toluene, ethyl acetate.This is because throughput rate, operation, economy are outstanding.

The concentration of above-mentioned polymer solution (1-A) is preferably 15～45 weight %, further preferred 20～40 weight %.By the concentration that makes polymer solution (1-A) is above-mentioned scope, outstanding to the screening characteristics of base material, and its result can obtain the outstanding adhesive phase of surface uniformity.

B-3. the cross-linking method of adhesive composition (the formation method of adhesive phase)

As making the crosslinked method of above-mentioned adhesive composition, can adopt the method for any appropriate.The preferred method that adhesive composition is heated of using.Heating-up temperature is preferably 50 ℃～200 ℃, and more preferably 70 ℃～190 ℃, be preferably 100 ℃～180 ℃ especially, most preferably be 120 ℃～170 ℃.By making heating-up temperature is above-mentioned scope, and the very fast generation of cross-linking reaction of (methyl) acrylic acid series polymeric compounds (A) and superoxide (B) can obtain having the bonding agent of outstanding adhesion characteristic.And then can suppress subsidiary reaction.To being not particularly limited heat time heating time, but be preferably 5 seconds～20 minutes, more preferably 5 seconds～10 minutes, be preferably 10 seconds especially～5 minutes.By making heat time heating time is above-mentioned scope, can more effectively carry out the cross-linking reaction of (methyl) acrylic acid series polymeric compounds (A) and superoxide (B).

As the object lesson of the formation method of adhesive phase, can enumerate the method that contains following operation 1C and operation 1D and prepare.

Operation 1C: on base material the coating above-mentioned polymer solution (1-B) operation,

Operation 1D: for example under 50 ℃～200 ℃ in operation 1C, form be coated with application heat, dry and form the operation of adhesive phase on the surface of base material.

Operation 1C obtains film like and is coated with application and carries out in order to launch polymer solution thinly on base material.Operation 1D is in order to make the solvent evaporation that is coated with application and to make superoxide and crosslinked polymer carries out.Wherein, the drying of operation 1D for example can be used a plurality of temperature control devices of setting different temperatures for, and the multistage carries out.Utilize such method, can effectively obtain the little adhesive phase of thickness deviation, suitably carry out the cross-linking reaction of superoxide and polymkeric substance simultaneously, can obtain the outstanding adhesive phase of adhesion characteristic.

As the method for the above-mentioned polymer solution of coating (1-B) on base material, adopt the application pattern of the coating machine that has used any appropriate.As coating machine, for example can enumerate reverse roll coater, just change roll coater, photogravure coating machine, scraper coating machine, rod and be coated with machine, seam hole (slot orifice) coating machine, curtain coater, spraying and applying machine, gas scraper coating machine, touch coating machine, dip coater, droplet applying machine, scraper plate coating machine, curtain coating coating machine, flush coater, spin coater, extrusion coating machine, hot melt coating machine etc.Preferred oppositely roll coater, photogravure coating machine, seam hole coating machine, curtain coater, spraying and applying machine.This is because can obtain the outstanding coated film of surface uniformity.

As above-mentioned base material, can select the base material of any appropriate.The preferred macromolecule membrane that uses.This is because can carry out the roller making and can increase substantially throughput rate.Base material can be a phase separation layer described later.Preferred substrates is used the base material of the surface of a side of coat polymers solution (1-B) at least being implemented lift-off processing.This is because the base material of so being implemented lift-off processing can be used as the release liner performance function of the polaroid (adhesive phase) that has phase separation layer.As object lesson, can enumerate the pet film of handling with the silicone-based remover.Wherein, release liner, is stripped from by in opticses such as (adhesive phase is being layered in before) liquid crystal cells before the practicality usually at the polaroid that has phase separation layer.

As being used to heat or the temperature control device of dry above-mentioned adhesive composition, can suitably select suitable temperature control device.The said temperature control gear for example can enumerate hot blast or cold wind carry out round-robin air circulating type constant temperature oven, utilized microwave or far infrared etc. well heater, be heated to be the methods such as roller, heat pipe roller or metal tape that adjustment is used.

B-4. adhesive phase and phase separation layer is stacked

The adhesive phase that utilizes above-mentioned operation 1A～operation 1D to obtain preferably is layered on the phase separation layer in advance.For example, utilize the method that contains following operation 1E to be layered on the phase separation layer.

Operation 1E: the adhesive phase that is formed on substrate surface that will obtain in operation 1D is layered on the phase separation layer and obtains the operation of duplexer.

Utilize such method, the optical characteristics that can obtain phase separation layer is difficult to the polaroid that has phase separation layer and the liquid crystal panel that change and have outstanding optical characteristics.And then, can obtain surface uniformity outstanding polaroid that has phase separation layer and liquid crystal panel.When stacked, adhesive phase can be layered in after base material is peeled off on the phase separation layer, can also the limit peels off boundary layer from base material and is stacked on the phase separation layer, it is peeled off from base material after can also be on being laminated in phase separation layer.

When above-mentioned adhesive composition contained the isocyanates based compound, above-mentioned laminating method preferably contained following operation 1F.

Operation 1F: the duplexer that will obtain in operation 1E is preserved 3 days operation at least.

Above-mentioned operation 1F is used to make above-mentioned adhesive phase slaking.In this manual, " being also referred to as slaking (ageing: aging) " is meant diffusion or the chemical reaction that carries out the material that contains in the adhesive phase, to obtain preferred character, state.

As the temperature that makes above-mentioned adhesive phase slaking (curing temperature), the kind, curing time that can utilize polymkeric substance or crosslinking chemical etc. suitably regulated.Be preferably 10 ℃～80 ℃, more preferably 20 ℃～60 ℃, be preferably 20 ℃～40 ℃ especially.By making curing temperature, can obtain having the adhesive phase of stable adhesion characteristic in above-mentioned scope.As the time that makes above-mentioned adhesive phase slaking (curing time), can suitably regulate according to the kind of polymkeric substance or crosslinking chemical, curing temperature etc.Curing time was preferably more than 3 days, more preferably more than 5 days, was preferably especially more than 7 days.By making the curing time is above-mentioned scope, can obtain having the adhesive phase of stable adhesion characteristic.

Example about the formation method of above-mentioned adhesive phase describes with reference to Fig. 3.For example, base material 302 spins portion 301 from first and is spun, with coating portion 303 coating above-mentioned polymer solutions (1-B).The application that is coated with that is coated in substrate surface is sent to temperature control device (drier) 304, and for example heating, drying under 50 ℃～200 ℃ form adhesive phase.Phase separation layer spins portion 306 from second and is spun, and is layered on the above-mentioned adhesive phase with stacked roller 307,308.The sandwich 309 of phase separation layer that so obtains and adhesive phase and base material 302 is reeled by coiling portion 310.Wherein, when base material 302 for example was the pet film of handling with the silicone-based remover, base material 302 can directly be used as release liner.

C. phase separation layer

Above-mentioned phase separation layer 20 contains resin bed 21 and tilted alignment layer 22.Below each layer described.

C-1. resin bed

Above-mentioned resin bed 21 can be selected any appropriate resin layer.The index ellipsoid of preferred resin layer has the relation of nx 〉=ny＞nz.Preferred 20～100 μ m of the thickness of resin bed.By with the thickness setting of resin bed in such scope, can obtain the outstanding phase separation layer of physical strength.

The preferred resin layer is the macromolecule membrane that contains thermoplastic resin.As thermoplastic resin, optimum fiber prime system resin.As cellulose-based resin, can adopt the cellulose-based resin of any appropriate.Preferred part or all cellulose organic ester that is replaced by acetyl group, propiono and/or butyl that uses cellulosic hydroxyl.As object lesson, can enumerate cellulose acetate, cellulose propionate, cellulose butyrate, cellulose-acetate propionate, cellulose acetate-butyrate etc.The method that cellulose-based resin so for example can utilize the spy to open record in 2001-188128 communique [0040]～[0041] obtains.

When above-mentioned cellulose-based resin contained acetyl group, its degree of substitution with acetyl group was preferably 1.5～3.0, and more preferably 2.0～2.9, be preferably 2.4～2.9 especially.When above-mentioned cellulose-based resin contained propiono, its propiono degree of substitution was preferably 0.5～3.0, and more preferably 1.0～2.9, be preferably 2.3～2.8 especially.When above-mentioned cellulose-based resin was replaced by acetyl group and propiono, the summation of its degree of substitution with acetyl group and propiono degree of substitution was preferably 1.5～3.0, and more preferably 2.0～3.0, be preferably 2.4～2.9 especially.At this moment, degree of substitution with acetyl group is preferably 0.1～1.5, and the propiono degree of substitution is preferably 1.5～2.9.By using so cellulose-based resin, can make the thinner phase separation layer that satisfies thickness direction phase difference value described later.

Wherein, degree of substitution with acetyl group or propiono degree of substitution are meant the number that the hydroxyl that connects on 2,3,6 the carbon in the cellulose skeleton is replaced by acetyl group (or propiono).In the optional position of 2,3,6 carbon of cellulose skeleton, acetyl group (or propiono) can be setovered, and can on average exist in addition.Above-mentioned degree of substitution with acetyl group can be obtained by ASTM-D817-91 (test method(s)s of cellulose acetate etc.).In addition, above-mentioned propiono degree of substitution can be obtained by ASTM-D817-96 (test method(s)s of cellulose acetate etc.).

Above-mentioned macromolecule membrane can also contain any proper additive.As adjuvant, for example can enumerate plastifier, thermal stabilizer, light stabilizer, lubricant, antioxidant, ultraviolet light absorber, fire retardant, colorant, antistatic agent, appearanceization agent mutually, crosslinking chemical, tackifier etc.Content of additive can be set suitable amount according to purpose.Content is preferably greater than 0 and be below 20 weight portions with respect to above-mentioned cellulose-based resin 100 weight portions.

Above-mentioned cellulose-based resin can directly use commercially available product.And then, can also implement to use after the suitable arbitrarily polymer modification to commercially available product.As the object lesson of polymer modification, can enumerate copolymerization, crosslinked, the modification of molecular end, modification of legislate etc.As the object lesson of commercially available product, can enumerate the cellulose-acetate propionate resin (trade name of Daicel Finechem (strain) system; 307E-09,360A-09,360E-16), the cellulose acetate (trade name of EASTMAN corporate system; CA-398-30, CA-398-30L, CA-320S, CA-394-60S, CA-398-10, CA-398-3, CA-398-30, CA-398-6), the cellulose butyrate (trade name of EASTMAN corporate system; CAB-381-0.1, CAB-381-20, CAB-500-5, CAB-531-1, CAB-551-0.2, CAB-553-0.4), the cellulose-acetate propionate (trade name of EASTMAN corporate system; CAP-482-0.5, CAP-482-20, CAP-504-0.2) etc.

The weight-average molecular weight of above-mentioned cellulose-based resin (Mw) is preferably 20000～1000000, and more preferably 25000～800000, be preferably 30000～600000 especially.So long as the weight-average molecular weight of above-mentioned scope, just can obtain the outstanding resin of operability of the outstanding and dissolubility of physical strength, mouldability, curtain coating.

The glass temperature of above-mentioned cellulose-based resin (Tg) is preferably 110 ℃～185 ℃, more preferably 120 ℃～170 ℃, is preferably 125 ℃～150 ℃ especially.If Tg is more than 110 ℃, can obtain the macromolecule membrane of good thermal stability, if Tg is below 185 ℃, can obtain the outstanding resin of processing and forming type.

As the method that obtains above-mentioned macromolecule membrane, can adopt suitable method for processing forming arbitrarily.As method for processing forming, for example can enumerate compression forming method, transfer molding method, injection moulding, extrinsion pressing, blow molding method, powder compacting method, the FRP method of forming, solvent casting method etc.Wherein, preferred solvent casting method.This is because can obtain flatness, macromolecule membrane that optical homogeneity is outstanding.

Above-mentioned macromolecule membrane can directly use commercially available product.And then, also can implement commercially available product to use after the secondary processing such as stretch processing, shrink process.As the object lesson of commercially available product, can enumerate the FUJITAC series (trade name of Fujiphoto (strain) system; ZRF80S, TD80UF), the trade name " KC8UX2M " of KonicaMinolta Opto (strain) system etc.

C-2. tilted alignment layer

Above-mentioned tilted alignment layer 22 is the layers by the liquid crystalline composition that contains discoid compound forms and discoid compound run-off the straight is orientated.By possessing the phase separation layer that contains such tilted alignment layer, can obtain picture contrast outstanding polaroid that has phase separation layer and liquid crystal panel.In this manual, " liquid crystalline composition " is meant and presents the compound that liquid crystal phase shows liquid crystal liquid crystal property." tilted alignment " can be liquid crystal molecule with certain angle tilt and the state (so-called inclination uniaxial orientation) arranged in same orientation, can also be liquid crystal molecule at the angle of inclination of thickness direction (tilt angle) continuously or the state (so-called hybrid orientation) that increases or reduce off and on.

The thickness of above-mentioned tilted alignment layer is preferably 1～5 μ m.By with the thickness setting of tilted alignment layer in such scope, can obtain objective optics characteristic (phase differential).And then, be used for can helping slimming under the situation of liquid crystal panel.

As above-mentioned discoid compound, be molecule with discoideus core, so long as show plectane phase and/or discoid nematic liquid crystal molecule, just can adopt suitable compound arbitrarily.What discoid compound was representative is to have 2～8 side chains to be combined into radial molecule with ehter bond or ester bond in discoideus central core.As central core, for example can enumerate distribution " liquid crystal dictionary " (1989), training wind shop p.22 Fig. 1 record, benzene, benzophenanthrene, toluxene, pyrans, Le Figarole, porphyrin, metal complex etc.Discoid compound preferably has the benzophenanthrene based compound of benzophenanthrene as central core.Wherein, preferably use the benzophenanthrene based compound of following general formula (I) expression.

[changing 1]

N in the above-mentioned general formula (I) is 2～10 integer.N is preferably 4～8, and more preferably 4～6, be preferably 6 especially.

As the method that makes above-mentioned discoid compound tilted alignment, can adopt suitable orientation process method arbitrarily.As the object lesson of orientation process method, can enumerate oblique evaporation method, optical alignment method, rubbing manipulation etc.The oblique evaporation method is representative is with the method for oxide evaporations such as monox to the substrate from oblique.In the method, by selecting deposition angles or evaporation number of times etc., can suitably regulate the angle of inclination of liquid crystal molecule.Optical alignment method for example is as CMC publication " functional material " Vol.25No.12 (2005) p.15～p.21 puts down in writing, from the oblique method that the reactive alignment films that is formed on substrate surface is shone polarized light or nonpolarized light.In the method, the irradiating angle by selecting polarized light or nonpolarized light, irradiation time etc. can suitably be regulated the angle of inclination of liquid crystal molecule.What rubbing manipulation was representative is with the method for cloth such as cotton, nylon, rayon along a direction wiping substrate or alignment layer surface.

Above-mentioned tilted alignment layer 22 is the layer that obtains after the liquid crystalline composition immobilization with tilted alignment in actual applications.As immobilized object lesson, can enumerate curing, sclerosis etc.Solidify and to be meant the liquid crystalline composition cooling of softening, fusion or solution state and to solidify.Sclerosis is meant part or all crosslinked insoluble not molten state or the indissoluble infusibility state of becoming that utilizes heat, catalyzer, light and/or radioactive ray to make liquid crystalline composition.Therefore, the liquid crystalline composition that is immobilized also can not show liquid crystal liquid crystal property.As the object lesson of the situation that does not show liquid crystal liquid crystal property, can enumerate and utilize photopolymerization etc. that liquid crystalline composition is formed cancellated situation.

As making the immobilized method of above-mentioned liquid crystalline composition, can adopt suitable method arbitrarily.Below, the method that makes its curing, the method for sclerosis are specifically described respectively.

As the method that above-mentioned liquid-crystal composition is solidified, for example can utilize the method that contains following operation 2A～operation 2C to obtain.

Operation 2A: the operation that the surperficial implementation orientation of base material (supporter) is handled,

Operation 2B: the solution of the substrate surface coated with liquid crystal composition of handling to implementation orientation or the operation that dispersion liquid makes its orientation,

Operation 2C: make the dry operation that forms cured layer of above-mentioned liquid crystalline composition.

Make the method for above-mentioned liquid crystalline composition sclerosis, for example except above-mentioned operation 2A～operation 2C, can also utilize the method that comprises following operation 2D to obtain.

Operation 2D: the operation that makes this liquid crystalline composition sclerosis to the cured layer irradiation ultraviolet radiation that in above-mentioned operation 2C, obtains.

At this moment, preferably use the discoid compound of display light bridging property, perhaps in above-mentioned liquid crystalline composition, add the compound of photocrosslinking reaction.

As the discoid compound of above-mentioned display light bridging property, for example can enumerate benzophenanthrene based compound with above-mentioned general formula (I) expression.As the compound of above-mentioned photocrosslinking reaction, can enumerate the acrylic resin of a sense, two senses or trifunctional.

As the phase separation layer 20 that contains resin bed 21 and tilted alignment layer 22, can directly use commercially available product.Perhaps, can also implement to use after the suitable arbitrarily secondary processing to commercially available product.As commercially available product, can enumerate the WV series thin film of Fujiphoto (strain) system etc.Wherein, preferably use WV film EA.

Above-mentioned phase separation layer 20 can also contain random layer.For example, between resin bed 21 and tilted alignment layer 22, can contain the orientation rete that is useful on the liquid crystalline composition generation orientation that makes formation tilted alignment layer 22.In addition, can also contain to be useful on and make bonding adhesive linkage of each layer or tackifier coating.And then phase separation layer can be implemented surface treatment.By implementing surface treatment, can improve connecting airtight property with above-mentioned adhesive phase 10, polariscope 30.As the surface-treated object lesson, can enumerate corona treatment, plasma treatment, glow discharge processing etc.

C-3. resin bed and tilted alignment layer is stacked

As the laminating method of above-mentioned resin bed and above-mentioned tilted alignment layer, can adopt suitable method arbitrarily.As the object lesson of laminating method, can enumerate the coating liquid (solution of above-mentioned liquid-crystal composition or dispersion liquid) from the tilted alignment layer to the surface applied of resin bed and the immobilized method that form.Preferably in the alignment films that on above-mentioned resin bed, is formed for making above-mentioned liquid-crystal composition orientation before the coating liquid coating in advance.As other laminating methods, can enumerate above-mentioned coating liquid being coated in base material (for example polyethylene terephthalate etc.) and make its immobilization and after forming the tilted alignment layer, this tilted alignment layer is transferred to the method on the surface of above-mentioned resin bed by adhesive linkage.At this moment, can want the surface of transfer printing tilted alignment layer to be pre-formed tackifier coating, can also implement suitable surface treatment arbitrarily the pre-of resin bed.As the surface-treated object lesson, can enumerate corona treatment.Wherein, above-mentioned base material can be peeled off simultaneously in the front and back of transfer printing or with transfer printing usually.

C-4. the optical characteristics of phase separation layer

The Re[590 of above-mentioned phase separation layer 20] can set suitable value arbitrarily for according to purpose.Preferred 20～80nm, more preferably 28～70nm is preferably 36～60nm especially.By making Re[590] be above-mentioned scope, under the situation of oblique observation picture, no matter observe from 360 ° arbitrary orientation, can obtain the certain liquid crystal indicator of contrast ratio.Wherein, Re[590] average tilt angle that can be by suitably selecting phase separation layer or the kind of thickness, above-mentioned discoid compound, use level etc., be adjusted to the value that needs.

The Rth[590 of above-mentioned phase separation layer] can set suitable value arbitrarily for according to purpose.Preferred 100～300nm, more preferably 110～190nm is preferably 120～180nm especially.By making Rth[590] be above-mentioned scope, under the situation of oblique observation picture, no matter observe from 360 ° arbitrary orientation, can obtain the certain liquid crystal indicator of contrast ratio.Wherein, Rth[590] can be adjusted to the value that needs by the thickness of suitable selection phase separation layer, the kind of adding the adjuvant in the phase separation layer to, use level etc.

The Nz coefficient of above-mentioned phase separation layer can be set suitable value arbitrarily for according to purpose.Preferred 2～8, more preferably 2～6, be preferably 2～4.2 especially, most preferably be 2～4.The Nz coefficient is to utilize formula: Rth[590]/Re[590] value calculated.By making the Nz coefficient is above-mentioned scope, can obtain under the situation of oblique observation picture, no matter observes the liquid crystal indicator that contrast ratio is all certain from 360 ° arbitrary orientation.Wherein, average tilt angle that the Nz coefficient can be by suitable selection phase separation layer or thickness, the kind of above-mentioned discoid compound, use level wait and regulate.

The average tilt angle of above-mentioned phase separation layer can be set suitable value arbitrarily for according to purpose.Preferred 8～24 °, more preferably 10～20 °, be preferably 12～18 ° especially, most preferably be 14～18 °.By making the average tilt angle is above-mentioned scope, can obtain the high liquid crystal indicator of oblique contrast ratio.Wherein, in this manual, " average tilt angle " is meant the statistics mean value at angle of inclination of each molecule of discoid compound.

D. polariscope

In this manual, polariscope is meant the element that natural light or polarized light can be converted to random polarization light.As above-mentioned polariscope 30, can adopt suitable polariscope arbitrarily according to purpose.Preferred polariscope is for converting natural light or polarized light to the polariscope of rectilinearly polarized light.2 polarized light components that such polariscope is orthogonal the light branch of incident usually pass through a side polarized light component, and with the opposing party's polarized light component absorption, reflection and/or scattering.Above-mentioned polariscopic thickness is preferably 5～50 μ m, more preferably 20～40 μ m.

Above-mentioned polariscope is that the transmitance (hereinafter referred to as the monomer transmitance) of the light measurement of 550nm is preferably more than 40% with wavelength down at 23 ℃, more preferably more than 42%.Wherein, the theoretical upper limit of monomer transmitance is 50%, and practical upper limit is 46%.

Above-mentioned polariscope is that the degree of polarization of the light measurement of 550nm is preferably more than 99.8% with wavelength down at 23 ℃, more preferably more than 99.9%.By degree of polarization being set in the above-mentioned scope, can obtain the high liquid crystal indicator of contrast ratio of frontal.Wherein, the theoretical upper limit of above-mentioned degree of polarization is 100%.

Above-mentioned polariscopic tone based on State Bureau of Standardization (NBS); A value (monomer a value) is preferably-more than 2.0, more preferably-more than 1.8.In addition, above-mentioned polariscopic tone based on State Bureau of Standardization (NBS); B value (monomer b value) is preferably below 4.2, more preferably below 4.0.Make polariscopic a value and b value near 0 more, just can obtain the bright display device of display image more.Therefore, the ideal value of a value and b value is 0.

As above-mentioned polariscope, can select the film of any appropriate.It is the oriented film of major component that polariscope is preferably with the polyvinyl alcohol resin that contains iodine or dichroic dye.Wherein, in this manual, " oriented film " is meant under suitable temperature and applies tension force improves the orientation of molecule along draw direction macromolecule membrane to the film that does not stretch.

Above-mentioned polyvinyl alcohol resin can be that the polymkeric substance saponification that monomer obtains obtains by making the polymerising ethylene ester.As vinyl acetate is monomer, for example can enumerate vinyl formate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, benzoic acid vinyl acetate, trimethylace tonitric vinyl acetate, tertiary ethylene carbonate etc.

The average degree of polymerization of above-mentioned polyvinyl alcohol resin can suitably be selected according to purpose.Average degree of polymerization is preferably 1200～3600.Wherein, average degree of polymerization can be that benchmark is obtained with JIS K 6726-1994.

The saponification degree of above-mentioned polyvinyl alcohol resin is preferably 95.0～99.9%.By making saponification degree is above-mentioned scope, can obtain the outstanding polariscope of permanance.Wherein, saponification degree can be that benchmark is obtained with JIS K 6726-1994.

With above-mentioned polyvinyl alcohol resin is the macromolecule membrane of major component, preferably contains polyvalent alcohol as plastifier.This is because can further improve the dyeability or the stretchability of film.As polyvalent alcohol, for example can enumerate ethylene glycol, glycerine, propylene glycol, diglycol, triethylene glycol, tetraethylene glycol, trimethylolpropane etc.They can use separately, can also be used in combination more than 2 kinds.The content of polyvalent alcohol is preferably greater than 0 and be below 30 weight portions with respect to polyvinyl alcohol resin 100 weight portions.

With above-mentioned polyvinyl alcohol resin is the macromolecule membrane of major component, preferably contains surfactant.This is because can further improve the dyeability or the stretchability of film.The preferred nonionic surfactant of surfactant.As nonionic surfactant, for example can enumerate lauric acid diethyl amide, cocoanut fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, lauric acid list isopropanol amide, oleic acid list isopropanol amide etc.The content of surfactant is preferably greater than 0 and be below 5 weight portions with respect to polyvinyl alcohol resin 100 weight portions.

As obtaining with above-mentioned polyvinyl alcohol resin is the method for the macromolecule membrane of major component, can adopt suitable shaping operation method arbitrarily.As the object lesson of shaping operation method, can enumerate the method that the spy opens record in the 2000-315144 communique [embodiment 1].

As being the macromolecule membrane of major component, can directly use commercially available product with above-mentioned polyvinyl alcohol resin.As the object lesson of commercially available product, can enumerate the trade name " Kuraray vinylon film " of (strain) KURARAY system, the trade name " Tohcello vinylon film " of Tohcello (strain) system, " day is closed the vinylon film " of Japanese synthetic chemical industry (strain) system etc.

Above-mentioned dichroic dye can use suitable dyestuff arbitrarily.In this manual, " dichromatism " be meant optical axis direction with the different optical anisotropy of absorption of this both direction glazing of direction of its quadrature.As dichroic dye, for example can enumerate red BR, red LR, red R, pink colour LB, pinkish red BL, purplish red GS, sky blue LG, lemon yellow, blue BR, blue 2R, navy blue RY, green LG, purple LB, purple B, black H, black B, black GSP, yellow 3G, yellow R, orange LR, orange 3R, scarlet GL, scarlet KGL, Congo red, blue GL, the Su Pula orange of blue G, Su Pula of brilliant violet BK, Su Pula GL, direct sky blue, chlorazol fast orange d S and fast black etc.

Example about above-mentioned method for manufacturing polarizer describes with reference to Fig. 4.For example, to spin with the macromolecule membrane 501 that polyvinyl alcohol resin is tieed up major component from the portion of spinning 500, be immersed in iodine aqueous solution and bathe in 510, with speed ratio different roller 511 and 512 along film length direction give tension force on one side, supply in swelling and dyeing process on one side.Then, be immersed in the bath 520 of the aqueous solution that contains boric acid and potassium iodide, with speed ratio different roller 521 and 522 along film length direction apply tension force on one side, supply in crosslinking Treatment on one side.The film that is implemented crosslinking Treatment is submerged in by roller 5321 and 532 in the water-soluble bath of liquid 530 that contains potassium iodide, is supplied to handle in washing.With regard to being implemented the film that washing handles, for example by being dried moisture rate is adjusted to 10～30% with drier 540, and by coiling portion 560 coilings.Polariscope 550 can be by through these operations, and will be that the macromolecule membrane 501 of major component stretches 5 times～7 times and obtains with the polyvinyl alcohol resin.

D-1. polariscope and phase separation layer is stacked

As the method for stacked above-mentioned polariscope 30, can adopt suitable method arbitrarily.Preferred polariscope 30 is attached on the above-mentioned phase separation layer 20 by adhesive linkage (not shown).In this manual, " adhesive linkage " is meant the face that engages adjacent optics and face and to be enough to practical bonding force and bonding time with its incorporate layer.As adhesive linkage, for example can enumerate bond layer, adhesive phase, tackifier coating etc.

Above-mentioned adhesive linkage for example is to form tackifier coating on the surface of adherend and form bond layer and the such sandwich construction of adhesive phase thereon, can also be that the thin layer of identification with the naked eye (is also referred to as hair line: hair line).By laminated polarizing mirror like this and phase separation layer, in the time of in being encased in liquid crystal indicator, can prevent this polariscopic absorption axes deviation in driction assigned position, prevent perhaps that polariscope and phase separation layer from friction taking place and impaired.And then, because can reduce the reflection that produces at the interface layer of polariscope and phase separation layer or the harmful effect of refraction, so can obtain showing the liquid crystal indicator of harsh image.

The thickness of above-mentioned adhesive linkage can be set suitable value arbitrarily for.Thickness is preferably 0.01～50 μ m.If the thickness of adhesive linkage in above-mentioned scope, can not produce on polariscope and float or peel off, can obtain being enough to practical bonding force and suitable bonding time.

The material that forms above-mentioned adhesive linkage can be selected the material of any appropriate according to the kind of adherend etc.The material that forms adhesive linkage preferably is the water soluble adhesive of major component with the polyvinyl alcohol resin.This be because, outstanding with polariscopic cementability, and operation, throughput rate, economy are outstanding.As above-mentioned be the water soluble adhesive of major component with the polyvinyl alcohol resin, can directly use commercially available product.Can be in commercially available product mixed solvent or adjuvant.As being the water soluble adhesive of major component, for example can enumerate the GOHSENOL series (trade name " NH-18S, GH-18S, T-330 etc. "), GOHSEFIMER series (trade name " Z-100, Z-200, Z-210 etc. ") of Japanese synthetic chemical industry (strain) system etc. with commercially available polyvinyl alcohol resin.

Above-mentioned adhesive linkage can be to make to cooperate crosslinking chemical to obtain the layer that composition is cross-linked to form in above-mentioned water soluble adhesive.Crosslinking chemical can adopt the material of any appropriate.As crosslinking chemical, for example can enumerate amines, aldehyde compound, methylol compound, epoxy compound, isocyanate compound, multivalent metal salt etc.Crosslinking chemical can directly use commercially available product.As the object lesson of commercially available product, can enumerate the amines trade name " Methaxylenediamine " of Mitsubishi's aerochemistry (strain) system, the aldehyde compound trade name " Griokizal " of Japanese synthetic chemical industry (strain) system, the methylol compound trade name " WATERSOL " of big Japanese ink (strain) system etc.

E. other the layer

In practicality, be provided with the protective seam (not shown) of any appropriate in a side that is not laminated with phase separation layer 20 of polariscope 30.By protective seam is set, can prevent the polariscope contraction or expansion, perhaps prevent UV-induced deterioration.The thickness of protective seam is preferably 20～100 μ m.By making thickness is above-mentioned scope, can obtain the outstanding polaroid that has phase differential of physical strength or permanance.

As above-mentioned protective seam, can adopt layer arbitrarily.It is the macromolecule membrane of resin or acrylic resin that protective seam preferably contains cellulose-based resin, norbornene resin, maleimide.Wherein, the preferred macromolecule membrane that contains cellulose-based resin that uses.As the macromolecule membrane that contains cellulose-based resin, preferred use with above-mentioned C-1 item in the identical film of film that illustrates.

When the polaroid that has phase separation layer of the present invention was used for liquid crystal indicator, the polaroid 100 that has phase separation layer was attached on the liquid crystal cells by adhesive phase 10.That is, above-mentioned protective seam is configured to towards identification side or backlight side.At this moment, for various purposes, can be at the outside of protective seam (not being laminated with a polariscopic side) configuration surface processing layer.

As above-mentioned surface-treated layer, for example can enumerate and be coated with processing layer, electrostatic prevention processing layer, antireflection (anti-reflection treated) layer, DIFFUSION TREATMENT (anti-glare treated) layer etc. firmly.By disposing such surface-treated layer, can prevent the pollution or the damage of picture, perhaps prevent to mirror picture and cause being difficult to observe display image owing to indoor fluorescent light or sunray.Surface-treated layer normally makes the treating agent that forms above-mentioned treated layers anchor at the layer on the surface of substrate film.Substrate film can the above-mentioned protective seam of double as.And then surface-treated layer for example can be to be laminated with to be coated with the such sandwich construction of processing layer firmly on the electrostatic prevention processing layer.

Above-mentioned protective seam can directly use the commercially available macromolecule membrane of implementing surface-treated layer.Perhaps, also can implement to use after the surface treatment arbitrarily to commercially available macromolecule membrane.As commercially available DIFFUSION TREATMENT (anti-glare treated), for example can enumerate day AG150, AGS1, AGS2, the AGT1 etc. of eastern electrician (strain) system.Handle (anti-reflection treatment) as commercially available antireflection, can enumerate day ARS, the ARC etc. of eastern electrician (strain) system.As being implemented the commercially available film that is coated with processing and electrostatic prevention processing firmly, for example can enumerate the trade name " KC8UX-HA " of Konica Minolta Opto (strain) system.As being implemented the commercially available surface-treated layer that antireflection is handled, for example can enumerate the ReaLook series of Japanese grease (strain) system etc.

Above-mentioned protective seam preferably is layered on the polariscope by adhesive linkage.As this adhesive linkage, for example can adopt the layer that in above-mentioned D-1 item, illustrates.

Except above-mentioned each layer, can be between each layer shown in Figure 1 and/or the outside dispose optical compensating layer, adhesive linkage etc. arbitrarily.In practicality, can dispose any release liner (not shown) in a side of the not laminated phase-difference layer 20 of adhesive phase 10 and obtain.

F. the integral body of liquid crystal panel constitutes

Fig. 5 is the fragmentary cross sectional view of the liquid crystal panel of preferred implementation of the present invention.Liquid crystal panel 101 possesses: liquid crystal cells 40, first polariscope 30 in the configuration of a side of liquid crystal cells 40, second polariscope 30 ' in the configuration of the opposite side of liquid crystal cells 40, first phase separation layer 20 of configuration between first polariscope 30 and liquid crystal cells 40, second phase separation layer 20 ' of configuration between second polariscope 30 ' and liquid crystal cells 40, first adhesive phase 10 of configuration between first phase separation layer 20 and liquid crystal cells 40, second adhesive phase 10 ' of configuration between second phase separation layer 20 ' and liquid crystal cells 40.That is, liquid crystal panel 101 possesses: liquid crystal cells 40, have the polaroid 100 of phase separation layer a side of liquid crystal cells 40 configuration of the present invention, at the polaroid 100 ' that has phase separation layer of the present invention of the opposite side configuration of liquid crystal cells.Wherein, about the polaroid 100 that has phase separation layer, 100 ' detailed description, as described in above-mentioned A～E item.

Except above-mentioned each layer, can be between each layer shown in Figure 5 and/or the outside dispose optical compensating layer, adhesive linkage etc. arbitrarily.

G. liquid crystal cells

The liquid crystal layer 43 that liquid crystal cells 40 has a pair of glass substrate 41,42 and disposes between this substrate as display medium.One side's substrate (active-matrix substrate) 41 is provided with on-off element (the representational TFT of being) that the electrooptics characteristic of liquid crystal is controlled and the sweep trace of gate signal is provided and the signal wire (all not shown) of source signal is provided to this on-off element.The opposing party's substrate (filter substrate) 42 is provided with color filter (not shown).Wherein, color filter can be arranged on the active-matrix substrate 41. Substrate 41 and 42 interval (cell gap) are by separator 44 Be Controlled.Be provided with the alignment films (not shown) that polyimide for example forms in substrate 41 and a side that contacts with liquid crystal layer 43 of 42.As the formation method of this alignment films, can adopt suitable orientation process method arbitrarily.As the object lesson of orientation process method, can enumerate rubbing manipulation, oblique evaporation method, optical alignment method etc.

As the drive pattern of liquid crystal cells 40,, just can adopt the drive pattern of any appropriate as long as can obtain effect of the present invention.As the object lesson of drive pattern, can enumerate STN (supertwist nematic phase: pattern super twisted nematic), TN (twisted-nematic phase: pattern twisted nematic), IPS (in-plane switching: pattern in-plane switching), VA (vertical calibration: verticalaligned) pattern, OCB (optical alignment birefringence: pattern optically aligned birefringence), HAN (mixes and calibrates nematic phase: pattern hybrid aligned nematic), (axially symmetry is calibrated micro unit to ASM: pattern axially symmetric aligned microcell).Preferred TN pattern.This be because, by with the present invention in the phase separation layer 20 (20 ') that uses and adhesive phase 10 (10 ') make up, can bring into play effect of the present invention better.

Fig. 6 is the concise and to the point stereographic map that the state of orientation to the liquid crystal molecule in the TN pattern describes.The direction of orientation of the direction of orientation of substrate 41 and substrate 42 is configured to basic quadrature.Because the direction of orientation of substrate 41 and 42 is quadrature basically, so when not applying voltage, shown in Fig. 6 (a), the liquid crystal molecule of liquid crystal layer 43 becomes the state of orientation that has 90 ° of torsion structures basically.That is, the orientation of liquid crystal molecule is according to along with the center away from liquid crystal layer, changes continuously gradually with the mode of the direction of orientation almost parallel of the substrate surface of subtend.Such state of orientation can realize by dispose the nematic crystal with positive dielectric constant anisotropy between the alignment films with fixed orientation restraint.Under such state, if make light incident from the face of a side substrate 41, liquid crystal molecule shows birefringence with respect to the light of the rectilinearly polarized light by inciding liquid crystal layer 43 behind first polariscope 30, and the polarization of incident light light state changes according to reversing of liquid crystal molecule.Light by liquid crystal layer when not applying voltage for example becomes the rectilinearly polarized light that makes its polarized light orientation half-twist, so can see through the demonstration (normal white mode) that second polariscope 30 ' obtains bright state.

As mentioned above, the liquid crystal molecule of liquid crystal layer 43 has positive dielectric constant anisotropy.Therefore, if apply voltage between electrode, then shown in Fig. 6 (b), the orientation of the liquid crystal molecule of liquid crystal layer 43 is perpendicular to substrate 41 and 42.Under such state, if make light incident from the face of a side substrate 41, then the light of the rectilinearly polarized light by inciding liquid crystal layer 43 behind first polariscope 30 advances along the long axis direction of vertical orientated liquid crystal molecule.Because the long axis direction at liquid crystal molecule does not produce birefringence, incident light advances according to the mode that does not change the polarized light orientation, is absorbed by second polariscope 30 ' that has with the absorption axes of first polariscope, 30 quadratures.When applying voltage, can obtain the demonstration of dark state thus.If be made as the state that does not apply voltage again, can return to the demonstration of bright state by orientation limitations power.In addition, apply the degree of tilt of Control of Voltage liquid crystal molecule, change the light intensity that sees through, can carry out gray scale and show from second polariscope 30 ' by change.

H. the optical axis of each layer concerns

Fig. 7 is the exploded perspective view that the optical axis to each layer of the liquid crystal panel 101 of pie graph 5 describes.With regard to the configuration of first polariscope 30 and second polariscope 30 ', representative is that they are configured to the mutually basic quadrature of its absorption axes.And then with regard to the configuration of second polariscope 30 ', representative is, and that it is configured to its absorption axes is substantially parallel with the direction of orientation of the substrate 42 of liquid crystal cells 40.

The basic quadrature of absorption axes direction of the slow axis direction of phase separation layer 20 (20 ') and polariscope 30 (30 ').In one embodiment, the slow axis direction of phase separation layer 20 (20 ') is with respect to a limit of liquid crystal panel (perhaps 135 °) at 45 (with reference to Fig. 2 (a)).In other embodiments, the slow axis direction of phase separation layer 20 becomes 90 ° of (perhaps 0 °) (with reference to Fig. 2 (b)) with respect to a limit of liquid crystal panel.Preferably shown in Fig. 4 (a), phase separation layer 20 is configured to its slow axis direction with respect to a limit of liquid crystal panel (perhaps 135 °) at 45.When adopting such configuration, can improve the contrast ratio of frontal especially.And then, when oblique observation picture,, also can obtain certain contrast ratio even if observe from 360 ° arbitrary orientation.

Wherein, the lamination order to each layer of constituting liquid crystal panel of the present invention is not particularly limited.

Below, utilize embodiment to specify the present invention, but the present invention is not limited to these embodiment.Wherein, each analytical approach of using in each embodiment and comparative example is as follows.

1. about adhesive phase

(1) assay method of confining force

As described later, make the test film S (polaroid that has phase separation layer) of 10mm * 30mm.As shown in Figure 8, at the upper end 10mm * 10mm that cures patch test sheet S on the plate P, obtain breadboard B by adhesive phase.Then, under 50 ℃, 5 atmospheric conditions, the breadboard B that obtains is implemented autoclave and handled 15 minutes, at room temperature placed then 1 hour.

Then, as shown in Figure 8, in 60 ℃ calibration cell, make the load W of the bottom load 500g of test film S, placed 1 hour.With the test film S and displacement amplitude (the confining force H that cures plate P after the placement of laser type creep testing machine mensuration _A).

(2) Determination of thickness method

Under the situation of thickness, use film to make ProductName " instantaneous multiple photometric system MCPD-2000 " with spectrophotometer [Da mound electronics (strain) less than 10 μ m] measure.Under thickness is situation more than the 10 μ m, use the digital micrometer " KC-351C type " of Anritsu system to measure.

(3) assay method of transmitance (T[590])

Using ultra-violet and visible spectrophotometer [Japanese beam split (strain) system ProductName " V-560 "], is that the light of 590nm is measured with the wavelength under 23 ℃.

(4) assay method of the gel fraction of bonding agent

With in advance the sample of the bonding agent of gravimetry be put in the container that is full of ethyl acetate, after 23 ℃ are down placed 7 days, take out bonding agent, wipe gravimetry after the solvent.Gel fraction is by following formula: { (W _A-W _B)/W _A* 100} obtains.Here, W _ABe the weight of putting into ethyl acetate adhesive phase before, W _BBe the weight of putting into ethyl acetate adhesive phase afterwards.

(5) assay method of glass temperature (Tg)

Use the differential scanning calorimeter ProductName " DSC220C " of Seiko electronics industry (strain) system, utilizing with JIS K 7121 is that the DSC method of benchmark is obtained.

(6) assay method of moisture rate

Adhesive phase put in 150 ℃ the air circulating type constant temperature oven, by through weight the slip { (W after 1 hour ₁-W ₂)/W ₁* 100} obtains.Here, W ₁Be the weight of putting into air circulating type constant temperature oven adhesive phase before, W ₂Be the weight of putting into air circulating type constant temperature oven adhesive phase afterwards.

(7) assay method of molecular weight

Utilize gel permeation chromatography (GPC) method to calculate for the standard test portion with the polystyrene.Particularly, utilize following device, utensil and condition determination to measure.Working sample use the bonding agent that obtains is dissolved in that tetrahydrofuran becomes the solution of 0.1 weight % and after leaving standstill an evening, filter with the membrane filter of 0.45 μ m after the filtrate that obtains.

Analytical equipment: TOSOH system " HLC-8120GPC "

Post: TSKgel SuperHM-H/H4000/H3000/H2000

Column dimension: respectively be 6.0mm I.D. * 150mm

Eluant: tetrahydrofuran

Flow: 0.6ml/min.

Detector: RI

Column temperature: 40 ℃

Injection rate IR: 20 μ l

2. about optical characteristics

(1) assay method of the mean refractive index of film

Use Abbe refractometer [ProductName " DR-M4 " of Atago (strain) system], obtain by the refractive index that with the wavelength is the light measurement of 589nm under 23 ℃.

(2) assay method of phase difference value (Re[590], Rth[590]) and average tilt angle

Use the trade name " KOBRA21-ADH " of prince's instrumentation machine (strain) system, measure with the light of 23 ℃ of wavelength 590nm.Wherein, use phase difference value (Re) in 23 ℃ the face of each wavelength, be sloping shaft phase difference value (R40), the thickness (d) of phase separation layer and the mean refractive index (n0) of phase separation layer that 40 degree measure that tilt with slow axis, utilize computer numerical to calculate and obtain nx, ny and nz, can calculate Rth.

(3) assay method of the monomer transmitance of polaroid, degree of polarization, tone a value, tone b value

Use spectrophotometer [color technical institute (strain) system ProductName " DOT-3 " in the village], under 23 ℃, measure.Degree of polarization can be by measuring polariscopic parallel transmitance (H ₀) and quadrature transmitance (H ₉₀), by formula: degree of polarization (%)={ (H ₀-H ₉₀)/(H ₀+ H ₉₀) ^1/2* 100 obtain.Parallel transmitance (H ₀) be 2 identical polariscopes to be overlapped into that its absorption axes is parallel to each other and the value of the transmitance of the parallel type layered polarization layer made.Quadrature transmitance (H ₉₀) be the value that 2 identical polariscopes is overlapped into the transmitance of the mutually orthogonal and orthogonal type layered polarization layer made of its absorption axes.Wherein, these transmitances are to carry out the Y value that visibility is proofreaied and correct by the 2 degree visuals field (illuminant-C) of JIS Z 8701-1982.

(4) assay method of contrast of LCD rate ratio

Make the bright lamp of backlight in 23 ℃ darkroom, then through after 30 minutes, use the ProductName " EZ Contrast160D " of ELDIM corporate system, the XYZ when measuring dialogue image and picture black and showing shows the Y value of system.Calculate oblique contrast ratio than [YW/YB] by Y value (YW) in the white image and the Y value (YB) in the picture black.Wherein, the long limit of liquid crystal panel is made as 0 ° at position angle, normal direction is made as 0 ° of polar angle.

Embodiment 1

(making of adhesive phase)

In the reaction vessel that possesses condenser pipe, nitrogen ingress pipe, thermometer and stirring apparatus, add butyl acrylate 99 weight portions, acrylic acid 4-hydroxy butyl ester 1.0 weight portions, 2,2-azoisobutyronitrile 0.3 weight portion and ethyl acetate, preparation solution.Then, the limit is blown into nitrogen in this solution, and stir on the limit, carries out 4 hours polyreactions under 60 ℃, obtains weight-average molecular weight and be 1,650,000 acrylic acid series copolymer.

Further add ethyl acetate and dilute in above-mentioned in the acrylate based copolymer that obtains, preparation total solid constituent concentration is the polymer solution (1-A) of 30 weight %.Then; in this polymer solution (1-A); with respect to acrylic ester copolymer 1 00 weight portion; cooperate the dibenzoyl peroxide [trade name " NYPER BO-Y " of Japanese grease (strain) system] of 0.3 weight portion, the trimethylolpropane XDI [trade name " Takenate D110N " of the military field chemistry of Mitsui (strain) system] of 0.18 weight portion, the silane coupling agent that contains acetoacetyl [always grinding the trade name " A-100 " of chemistry (strain) system] of 0.2 weight portion successively, preparation polymer solution (1-B).

The polymer solution (1-B) that uses the spraying and applying machine to obtain in above-mentioned is coated in the surface of base material (pet film of using the silicone-based remover to handle) equably.In 155 ℃ air circulating type constant temperature oven dry 70 seconds then, form adhesive phase on the surface of base material.Confining force (the H of the adhesive phase that obtains _A) be 120 μ m, confining force (H _B) be 80 μ m, and transmitance (T[590]) be 92%.Gel fraction is 84%, and glass temperature (Tg) is-38 ℃, and moisture rate is 0.25%.

(polariscopic making)

Use is combined with the dye bath (30 ℃ ± 3 ℃) of iodine and potassium iodide, uses the roller drawing machine to carrying out unilateral stretching to 2.5 times with polyvinyl alcohol (PVA) as the limit of dyeing, the macromolecule membrane of major component [trade name " 9P75R (thickness 75 μ m, average degree of polymerization=2400, saponification degree=99.9 mole %) " of KURARAY (strain) system] limit.Then, in the aqueous solution that is combined with boric acid and potassium iodide (60 ℃ ± 3 ℃), cross-linking reaction is carried out on the limit, and unilateral stretching is carried out on the limit, makes that polyvinyl alcohol film is 6 times of former length.In 50 ℃ ± 1 ℃ air circulating type constant temperature oven,, obtain polariscope with the film drying that obtains 30 minutes.

(phase separation layer)

As having resin bed and forming and this discoid compound carries out the phase separation layer of the tilted alignment layer of tilted alignment, use the trade name " WV film EA " of Fujiphoto (strain) system by the liquid crystalline composition that contains discoid compound.The Re[590 of this film] be 40nm, Rth[590] be 155nm, the Nz coefficient is 3.9, the average tilt angle is 16.0 °.

(having the making of the polaroid of phase separation layer)

Tilted alignment layer one side to above-mentioned phase separation layer implemented corona treatment (1.2kW/15m/ minute).At the folded adhesive phase that is formed at above-mentioned substrate surface of corona treatment surface layer, obtain duplexer A.At this moment, the laminating adhesive layer makes it become corona treatment face side.Then, in 70 ℃ air circulating type constant temperature oven with duplexer A slaking 7 days.Wherein, the thickness of adhesive phase is 21 μ m.Be layered in the polariscope that obtains in above-mentioned by polyethenol series bonding agent (thickness 0.1 μ m) in phase separation layer (resin bed) side of the duplexer A of slaking.And then, at polariscopic opposite side (side of not stacked duplexer A) stacked guard layer [cellulose triacetate film, Fujiphoto system, trade name: FUJITAC], obtain having the polaroid of phase separation layer by polyethenol series bonding agent (thickness 0.1 μ m).

(making of liquid crystal indicator)

Take out liquid crystal panel from the liquid crystal indicator [BenQ makes trade name " FP71E+ "] of the commercially available liquid crystal cells that contains the TN pattern, remove the optical thin films such as polaroid of configuration up and down fully at liquid crystal cells.The glass substrate of the liquid crystal cells that cleaning obtains (surface and the back side) obtains liquid crystal cells A.Be attached to the polaroid that has phase separation layer that obtains in above-mentioned in the both sides of liquid crystal cells A, obtain liquid crystal panel A.At this moment, as shown in Figure 7, paste according to the mode of each polariscope 30,30 ' the mutually basic quadrature of absorption axes.In addition, the absorption axes of pasting into polariscope 30 (30 ') is substantially parallel with the direction of orientation of the glass substrate 41 (42) of adjacent liquid crystal cells 40.The liquid crystal panel A that obtains is combined with back light unit, obtain liquid crystal indicator A.

Embodiment 2

Use is the trimethylolpropane XDI of 0.12 weight portion with respect to aforesaid propylene acid esters based copolymer 100 weight portions, make adhesive phase, in addition, with embodiment 1 the same polaroid and the liquid crystal indicator that has phase separation layer of making.Confining force (the H of the adhesive phase that obtains _A) be 150 μ m, confining force (H _B) be 100 μ m, and transmitance (T[590]) be 92%.Gel fraction is 82%, and glass temperature (Tg) is-38 ℃, and moisture rate is 0.25%.

Embodiment 3

Except using Fujiphoto (strain) system trade name " WV film SA ", with embodiment 1 the same polaroid and the liquid crystal indicator that has phase separation layer of making as the phase separation layer.The Re[590 of this film] be 35nm, Rth[590] be 155nm, the Nz coefficient is 4.43, the average tilt angle is 18.9 °.

Embodiment 4

Except using Fujiphoto (strain) system trade name " WV film A ", with embodiment 1 the same polaroid and the liquid crystal indicator that has phase separation layer of making as the phase separation layer.The Re[590 of this film] be 21.9nm, Rth[590] be 140nm, the Nz coefficient is 6.4, the average tilt angle is 15.2 °.

Comparative example 1

Use is the trimethylolpropane XDI of 0.02 weight portion with respect to aforesaid propylene acid esters based copolymer 100 weight portions, in addition, and with embodiment 1 the same polaroid and the liquid crystal indicator that has phase separation layer of making.Confining force (the H of the adhesive phase that obtains _A) be 380 μ m, confining force (H _B) be 250 μ m, and transmitance (T[590]) be 92%.Gel fraction is 72%, and glass temperature (Tg) is-38 ℃, and moisture rate is 0.27%.

Comparative example 2

Except not being provided with the phase separation layer, with embodiment 1 the same polaroid and the liquid crystal indicator made.

After backlight lighted soon the liquid crystal indicator of embodiments of the invention 1,3,4 and the liquid crystal indicator of comparative example 1,2, have good show uniformity comprehensively.

The field angle dependence of the contrast of the polaroid that has phase separation layer that obtains in embodiment 1,3,4 and the comparative example 2 is shown in the contrast contour map of Fig. 9.And then, the polar angle dependence and the position angle dependence of contrast ratio ratio is shown in Figure 10.Can be known clearly that by Fig. 9～10 liquid crystal indicator of embodiments of the invention is compared with the liquid crystal indicator of comparative example, positive contrast and oblique contrast both are outstanding.

In 60 ℃ air circulating type calibration cell, will use the liquid crystal panel keeping 100 hours that the polaroid that has phase separation layer of embodiment 1, embodiment 2 and comparative example 1 obtains, be fetched into 23 ℃ indoor then.This liquid crystal panel is made liquid crystal indicator as described above, observe whether when showing picture black, producing the demonstration inequality.Observation is to use 2 dimension look measure of spread devices [Minolta makes trade name " CA-1500 "], and is undertaken by in 23 ℃ darkroom display frame being taken.This observation photo is shown in Figure 11.As Figure 11 (a) with (b), the liquid crystal indicator of embodiment 1 and embodiment 2 has suppressed to show uneven well.On the other hand, shown in Figure 11 (c), the liquid crystal indicator of comparative example 1 all produces inequality in whole image.

Industrial utilizability

Polarizer with phase separation layer of the present invention, liquid crystal panel and liquid crystal indicator for example can To perform well in the OA equipment such as PC, notebook computer, duplicator, mobile phone, clock The mobile devices such as table, digital camera, personal digital assistant device (PDA), portable game machine, shooting Mechanical, electrically look, the home appliance such as micro-wave oven, anti-monitor (back monitor), onboard navigation system With vehicle mounted equipment such as monitor, audio devices,, supervise with presentation devices such as monitors with information in the shop Depending on guard equipment such as monitors, nurse nurse/Medical Devices such as using monitor, medical monitor etc.

Claims (20)

1. polaroid that has phase separation layer, wherein,

Have adhesive phase successively, contain the phase separation layer and the polariscope of resin bed and tilted alignment layer,

Confining force (the H of this adhesive phase under 60 ℃ _A) be below the 300 μ m,

The slow axis direction of this phase separation layer and the basic quadrature of this polariscopic absorption axes direction,

This tilted alignment layer is to be formed by the liquid crystalline composition that contains discoid compound, and this discoid compound is a tilted alignment.

2. the polaroid that has phase separation layer as claimed in claim 1, wherein,

Confining force (the H of described adhesive phase under 60 ℃ _A) and the confining force (H under 23 ℃ _B) poor (H _A-H _B) be below the 100 μ m.

3. as claim 1 or the 2 described polaroids that have phase separation layer, wherein,

The moisture rate of described adhesive phase is below 1.0%.

4. as any described polaroid that has phase separation layer in the claim 1～3, wherein,

The gel fraction of described adhesive phase is more than 75%.

5. as any described polaroid that has phase separation layer in the claim 1～4, wherein,

Described adhesive phase is that the adhesive composition that contains (methyl) acrylic acid series polymeric compounds (A) and superoxide (B) by making at least carries out crosslinked formation.

6. the polaroid that has phase separation layer as claimed in claim 5, wherein,

Described (methyl) acrylic acid series polymeric compounds (A) is the multipolymer of (methyl) alkyl acrylate (a1) and hydroxyl (methyl) acrylate (a2).

7. as claim 5 or the 6 described polaroids that have phase separation layer, wherein,

The use level of described superoxide (B) is 0.01～1 weight portion with respect to described (methyl) acrylic acid series polymeric compounds (A) 100 weight portions.

8. as any described polaroid that has phase separation layer in the claim 5～7, wherein,

Described adhesive composition also contains the isocyanates based compound.

9. the polaroid that has phase separation layer as claimed in claim 8, wherein,

The use level of described isocyanates based compound is 0.04～1 weight portion with respect to described (methyl) acrylic acid series polymeric compounds (A) 100 weight portions.

10. as any described polaroid that has phase separation layer in the claim 1～9, wherein,

The index ellipsoid of described resin bed has the relation of nx 〉=ny＞nz.

11. as any described polaroid that has phase separation layer in the claim 1～10, wherein,

Described resin bed is the polymeric membrane that contains cellulose-based resin.

12. as any described polaroid that has phase separation layer in the claim 1～11, wherein,

Described discoid compound is that benzophenanthrene is discoid compound.

13. as any described polaroid that has phase separation layer in the claim 1～12, wherein,

Phase differential Re[590 in the face of described phase separation layer] be 20～80nm.

14. as any described polaroid that has phase separation layer in the claim 1～13, wherein,

The thickness direction phase differential Rth[590 of described phase separation layer] be 100～300nm.

15. as any described polaroid that has phase separation layer in the claim 1～14, wherein,

The Nz coefficient of described phase separation layer is 2～8.

16. as any described polaroid that has phase separation layer in the claim 1～15, wherein,

The average tilt angle of described phase separation layer is 8～24.。

17. as any described polaroid that has phase separation layer in the claim 1～16, wherein,

Described polariscope is to be the oriented film of principal ingredient with the polyvinyl alcohol resin that contains iodine or dichroic dye.

18. a liquid crystal panel possesses:

Liquid crystal cells,

Be configured in a side of this liquid crystal cells and described adhesive phase is configured in the claim 1～17 of liquid crystal cell side any described polaroid that has a phase separation layer and

Be configured in the opposite side of this liquid crystal cells and described adhesive phase be configured to any described polaroid that has phase separation layer in the claim 1～17 of liquid crystal cell side.

19. liquid crystal panel as claimed in claim 18, wherein,

Described liquid crystal cells is the TN pattern.

20. a liquid crystal indicator, wherein,

Contain claim 18 or 19 described liquid crystal panels.

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